Poly[aquaneodymium(III)‐μ5‐2‐oxido‐5‐sulfonatobenzoato]

The title compound, [Nd(C₇H₃O₆S)(H₂O)]_n or [Nd(SSA)(H₂O)]_n (H₃SSA is 5‐sulfosalicylic acid), was synthesized by the hydrothermal reaction of Nd₂O₃ with H₃SSA in water. The compound forms a three‐dimensional network in which the asymmetric unit contains one Nd^III atom, one SSA ligand and one coordinated water mol­ecule. The central Nd^III ion is eight‐coordinate, bonded to seven O atoms from five different SSA ligands [Nd—O = 2.405 (4)–2.612 (4) Å] and one aqua O atom [Nd—OW = 2.441 (4) Å].     

Hydrated hexacyanometallate(III) salts of triaqua(18‐crown‐6)lanthanoid(III) and tetraaqua(18‐crown‐6)lanthanoid(III) cations containing nine‐ and ten‐coordinate lanthanoids

Tetraaqua(18‐crown‐6)cerium(III) hexacyanoferrate(III) dihydrate, [Ce(C₁₂H₂₄O₆)(H₂O)₄][Fe(CN)₆]·2H₂O, and tetraaqua(18‐crown‐6)neodymium(III) hexacyanoferrate(III) dihydrate, [Nd(C₁₂H₂₄O₆)(H₂O)₄][Fe(CN)₆]·2H₂O, are isomorphous and isostructural in the C2/c space group, where the cations, which contain ten‐coordinate lanthanoid centres, lie across twofold rotation axes and the anions lie across inversion centres. In these compounds, an extensive series of O—H...O and O—H...N hydrogen bonds links the components into a continuous three‐dimensional framework. Triaqua(18‐crown‐6)lanthanoid(III) hexacyanoferrate(III) dihydrate, [Ln(C₁₂H₂₄O₆)(H₂O)₃][Fe(CN)₆]·2H₂O, where Ln = Sm, Eu, Gd or Tb, are all isomorphous and isostructural in the P space group, as are triaqua(18‐crown‐6)gadolinium(III) hexacyanochromate(III) dihydrate, [Gd(C₁₂H₂₄O₆)(H₂O)₃][Cr(CN)₆]·2H₂O, and triaqua(18‐crown‐6)gadolinium(III) hexacyanocobaltate(III) dihydrate, [Gd(C₁₂H₂₄O₆)(H₂O)₃][Co(CN)₆]·2H₂O. In these compounds, there are two independent anions, both lying across inversion centres, and the lanthanoid centres exhibit nine‐coordination; in the crystal structures, an extensive series of hydrogen bonds links the components into a three‐dimensional framework.     

Dinuclear Complexes of Copper(I) with Crown Ether‐containing N‐Thiophosphorylated Bis‐thioureas and 2,2′‐Bipyridine or 1,10‐Phenanthroline: Synthesis,Characterization, and Picrate Extraction Properties

Reaction of O,O′‐diisopropylthiophosphoric acid isothiocyanate (iPrO)₂P(S)NCS with 1,10‐diaza‐18‐crown‐6, 1,7‐diaza‐18‐crown‐6, or 1,7‐diaza‐15‐crown‐5 leads to the N‐thiophosphorylated bis‐thioureas N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 ( H₂L^I ), N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐18‐crown‐6 ( H₂L^II ) and N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐15‐crown‐5 ( H₂L^III ). Reaction of the potassium salts of H₂L^I–III with a mixture of CuI and 2,2′‐bipyridine ( bpy ) or 1,10‐phenanthroline ( phen ) in aqueous EtOH/CH₂Cl₂ leads to the dinuclear complexes [Cu₂(bpy)₂L^I–III] and [Cu₂(phen)₂L^I–III] . The structures of these compounds were investigated by ¹H, ³¹P{¹H} NMR spectroscopy, and elemental analysis. The crystal structures of H₂L^I and [Cu₂(phen)₂L^I] were determined by single‐crystal X‐ray diffraction. Extraction capacities of the obtained compounds in comparison to the related compounds 1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(=CMe₂)CH₂P(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(S)NHP(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 towards the picrate salts LiPic, NaPic, KPic. and NH₄Pic were also studied.     

Controlled Synthesis of Heterotrimetallic Single‐Chain Magnets from Anisotropic High‐Spin 3 d–4 f Nodes and Paramagnetic Spacers

By using the node‐and‐spacer approach in suitable solvents, four new heterotrimetallic 1D chain‐like compounds (that is, containing 3d–3d′–4f metal ions), {[Ni(L)Ln(NO₃)₂(H₂O)Fe(Tp*)(CN)₃] ? 2 CH₃CN ? CH₃OH}_n (H₂L=N,N′‐bis(3‐methoxysalicylidene)‐1,3‐diaminopropane, Tp*=hydridotris(3,5‐dimethylpyrazol‐1‐yl)borate; Ln=Gd ( 1 ), Dy ( 2 ), Tb ( 3 ), Nd ( 4 )), have been synthesized and structurally characterized. All of these compounds are made up of a neutral cyanide‐ and phenolate‐bridged heterotrimetallic chain, with a {? Fe? C?N? Ni(? O? Ln)? N?C? }_n repeat unit. Within these chains, each [(Tp*)Fe(CN)₃]^? entity binds to the Ni^II ion of the [Ni(L)Ln(NO₃)₂(H₂O)]⁺ motif through two of its three cyanide groups in a cis mode, whereas each [Ni(L)Ln(NO₃)₂(H₂O)]⁺ unit is linked to two [(Tp*)Fe(CN)₃]^? ions through the Ni^II ion in a trans mode. In the [Ni(L)Ln(NO₃)₂(H₂O)]⁺ unit, the Ni^II and Ln^III ions are bridged to one other through two phenolic oxygen atoms of the ligand (L). Compounds 1 – 4 are rare examples of 1D cyanide‐ and phenolate‐bridged 3d–3d′–4f helical chain compounds. As expected, strong ferromagnetic interactions are observed between neighboring Fe^III and Ni^II ions through a cyanide bridge and between neighboring Ni^II and Ln^III (except for Nd^III) ions through two phenolate bridges. Further magnetic studies show that all of these compounds exhibit single‐chain magnetic behavior. Compound 2 exhibits the highest effective energy barrier (58.2 K) for the reversal of magnetization in 3d/4d/5d–4f heterotrimetallic single‐chain magnets.     

pH Dependent Synthesis of NdIII Coordination Compounds Based on Bifunctional 5‐(4‐Pyridyl)tetrazole‐2‐acetic Acid

The Nd^III coordination compounds [Nd(4‐pytza)₃(H₂O)₂] · 2H₂O ( 1 ) and [Nd(4‐pytza)₂(H₂O)₄]Cl · 2H₂O ( 2 ) [H4‐pytza = 5‐(4‐pyridyl)tetrazole‐2‐acetic acid] were synthesized by reactions of K4‐pytza and NdCl₃ · 6H₂O at different pH values. Single crystal X‐ray diffraction analysis reveals that 4‐pytza ligands in 1 in a μ_1,3‐COO syn‐syn or μ_1,1,3‐COO bridging mode coordinate to two central Nd^III atoms to display a dinuclear unit, which is connected by one of these 4‐pytza ligands acting in end‐to‐end bridging mode to form a 1D ladder‐like chain. Different from 1 , each 4‐pytza in 2 with a μ_1,3‐COO syn‐anti bridging mode coordinates to two Nd^III atoms to display a 1D zigzag chain. Furthermore, the luminescence properties of 1 and 2 were investigated at room temperature in the solid state.     

Synthesis and Characterization of [XeOXe]2+ in the Adduct‐Cation Salt, [CH3CN‐ ‐ ‐XeOXe‐ ‐ ‐NCCH3][AsF6]2

Acetonitrile and [FXeOXe‐ ‐ ‐FXeF][AsF₆] react at ?60 °C in anhydrous HF (aHF) to form the CH₃CN adduct of the previously unknown [XeOXe]²⁺ cation. The low‐temperature X‐ray structure of [CH₃CN‐ ‐ ‐XeOXe‐ ‐ ‐NCCH₃][AsF₆]₂ exhibits a well‐isolated adduct‐cation that has among the shortest Xe?N distances obtained for an sp‐hybridized nitrogen base adducted to xenon. The Raman spectrum was fully assigned by comparison with the calculated vibrational frequencies and with the aid of ¹⁸O‐enrichment studies. Natural bond orbital (NBO), atoms in molecules (AIM), electron localization function (ELF), and molecular electrostatic potential surface (MEPS) analyses show that the Xe?O bonds are semi‐ionic whereas the Xe?N bonds may be described as strong electrostatic (σ‐hole) interactions.     

The Building Block [FeIII(pzphen)(CN)4]– and its Lanthanide Complexes: Synthesis,Crystal Structure,and Magnetic Properties

The cyanide building block [Fe^III(pzphen)(CN)₄]^– and its four lanthanide complexes [{Fe^III(pzphen)(CN)₄}₂Ln^III(H₂O)₅(DMF)₃] · (NO₃) · 2(H₂O) · (CH₃CN) [Ln = Nd ( 1 ), Sm ( 2 ), DMF = dimethyl formamide] and [{Fe^III(pzphen)(CN)₄}₂Ln^III(NO₃)(H₂O)₂(DMF)₂](CH₃CN) [Ln = Gd ( 3 ), Dy ( 4 )] were synthesized and structurally characterized by single‐crystal X‐ray diffraction. Compounds 1 and 2 are ionic salts with two [Fe^III(pzphen)(CN)₄]^– cations and one Ln^III ion, but compounds 3 and 4 are cyano‐bridged Fe^III‐Ln^III heterometallic 3d‐4f complexes exhibiting a trinuclear structure in the same conditions. Magnetic studies show that compound 3 is antiferromagnetic between the central Fe^III and Gd^III atoms. Furthermore, the trinuclear cyano‐bridged Fe^III₂Dy^III compound 4 displays no single‐molecular magnets (SMMs) behavior by the alternating current magnetic susceptibility measurements.     

Design and Synthesis of Calixarene‐Based Bis‐alkynyl‐Bridged Dinuclear AuI Isonitrile Complexes as Luminescent Ion Probes by the Modulation of Au⋅⋅⋅Au Interactions

Two calixarene‐based bis‐alkynyl‐bridged Au^I isonitrile complexes with two different crown ether pendants, [{calix[4]arene‐(OCH₂CONH‐C₆H₄C≡C)₂}{Au(CNR)}₂] (R=benzo[15]crown‐5 ( 1 ); R=benzo[18]crown‐6 ( 2 )), together with their related crown‐free analogue 3 (R=C₆H₃(OMe)₂‐3,4) and a mononuclear gold(I) complex 4 with benzo[15]crown‐5 pendant, have been designed and synthesized, and their photophysical properties have been studied. The X‐ray structure of the ligand, calix[4]arene‐(OCH₂CONH‐C₆H₄C?CH)₂ has been determined. The cation‐binding properties of these complexes with various metal ions have been studied using UV/Vis, emission, ¹H NMR, and ESI‐MS techniques, and DFT calculations. A new low‐energy emission band associated with Au???Au interaction could be switched on upon formation of the metal ion‐bound adduct in a sandwich fashion.     

Poly[[tetraaquadi‐μ4‐glutarato‐μ2‐terephthalato‐dineodymium(III)] heptadecahydrate]

The title compound, [Nd₂(C₅H₆O₄)₂(C₈H₄O₄)(H₂O)₄]·17H₂O, obtained via hydrothermal reaction of Nd₂O₃ with glutaric acid and terephthalic acid, assembles as a three‐dimensional open framework with ten‐coordinate Nd–O polyhedra. The asymmetric part of the unit cell contains half a glutarate anion, a quarter of a terephthalate dianion, half an Nd^III cation, one coordinated water molecule and 4.25 solvent water molecules. Each [NdO₁₀] coordination polyhedron is comprised of six O atoms originating from four glutarate anions, two others from a terephthalate carboxylate group, which coordinates in a bidentate fashion, and two from water molecules. The Nd—O distances range from 2.4184 (18) to 2.7463 (18) Å. The coordination polyhedra are interconnected by the glutarate anions, extending as a two‐dimensional layer throughout the bc plane. Individual two‐dimensional layers are interlinked via terephthalate anions along the a axis. This arrangement results in rectangular‐shaped cavities with interstices of approximately 3.5 × 6 × 6.5 Å (approximately 140 ų), which are occupied by water molecules. The Nd^III cations, terephthalate anions, glutarate anions and one of the interstitial water molecules are located on special crystallographic positions. The Nd–terephthalate–Nd units are located across twofold rotation axes parallel to [100], with the Nd^III cations located directly on these axes. In addition, the terephthalate anion is bisected by a crystallographic mirror plane perpendicular to that axis, thus creating an inversion centre in the middle of the aromatic ring. The glutarate ligand is bisected by a crystallographic mirror plane perpendicular to (001). One of the solvent water molecules lies on a site of 2/m symmetry, and the symmetry‐imposed disorder of its H atoms extends to the H atoms of the other four solvent water molecules, which are disordered over two equally occupied and mutually exclusive sets of positions.     

Identification of the Structural Boundary between [Ln(18‐crown‐6)(NO3)3] and [Ln(NO3)3(H2O)3] · 18‐crown‐6 Motifs in the Lanthanide Series

Recrystallization of Ln(NO₃)₃ (Ln = Sm, Eu, Yb) in the presence of 18‐crown‐6 under aqueous conditions yielded [Ln(NO₃)₃(H₂O)₃] · 18‐crown‐6. X‐ray crystallography revealed isomorphous structures for each of the lanthanide complexes where [Ln(NO₃)₃(H₂O)₃] is involved in hydrogen bonding interactions with 18‐crown‐6. The transition point where the structural motif changes from [Ln(18‐crown‐6)(NO₃)₃] (with the metal residing in the crown cavity) to [Ln(NO₃)₃(H₂O)₃] · 18‐crown‐6 has been identified as at the Nd/Sm interface. A similar investigation involving [Ln(tos)₃(H₂O)₆] (tos = p‐toluenesulfonate) and 18‐crown‐6 were resistant to crown incorporation. X‐ray studies show extensive intra‐ and intermolecular hydrogen bonding is present.     

Potassium di­cyano­argentate(I) 1,4,7,10,13,16‐hexaoxa­cyclo­octadecane

The crystal structure of the title compound, K[Ag(CN)₂]·C₁₂H₂₄O₆, conventionally denoted K(18‐crown‐6)Ag(CN)₂, where 18‐crown‐6 is 1,4,7,10,13,16‐hexa­oxa­cyclo­octa­decane, is characterized by closely packed linear chains formed by the coordination of the nitrile N atoms of the [Ag(CN)₂]⁻ anions to the K⁺ cations. The K atoms lie on centers of inversion and are additionally bound to the six O atoms of the crown ether.     

A three‐component cocrystal: benzoyl(hydroxyimino)acetonitrile–18‐crown‐6–water (2/1/4)

In the title compound, 2C₉H₆N₂O₂·C₁₂H₂₄O₆·4H₂O, the 18‐crown‐6 (1,4,7,10,13,16‐hexaoxacyclooctadecane) molecule resides across a centre of inversion. The adduct exists as a molecular hydrogen‐bonded complex featuring integration of two kinds of synthons, viz. [(18‐crown‐6)(H₂O)₄] [O...O = 2.8645 (18)–2.9014 (18) Å] and an oxime/aqua ensemble, PhC(O)C(CN)NOH...OH₂ [O...O = 2.5930 (18) Å]. The reliability of the oxime/aqua motif, sustained by the highly acidic cyanooxime, is an essential factor in the construction of multicomponent cocrystals and the accommodation of oxime species in macrocyclic hosts. The supramolecular structure is generated by the alternation of hydrophilic [(18‐crown‐6)(H₂O)₄] layers and bilayers of benzoyl(hydroxyimino)acetonitrile molecules, resulting in stacking interactions between the phenyl and cyano groups of 3.666 (2) Å.     

Die Kristallstruktur der hydratisierten Cyanokomplexe NMe4MnII[(Mn, Cr)III(CN)6] · 3 H2O und NMe4Cd[MIII(CN)6] · 3 H2O (MIII = Fe,Co): Verwandte des Berliner Blaus

The Crystal Structure of the Hydrated Cyano Complexes NMe₄Mn^II[(Mn, Cr)^III(CN)₆] · 3 H₂O and NMe₄Cd[M^III(CN)₆] · 3 H₂O (M^III = Fe, Co): Compounds Related to Prussian Blue The crystal structures of the isotypic tetragonal compounds (space group I4, Z = 10) NMe₄Mn^II · [(Mn, Cr)^III(CN)₆] · 3 H₂O (a = 1653.2(4), c = 1728.8(6) pm), NMe₄Cd[Fe(CN)₆] · 3 H₂O (a = 1642.7(1), c = 1733.1(1) pm) and NMe₄Cd[Co(CN)₆] · 3 H₂O (a = 1632.1(2), c = 1722.4(3) pm) were determined by X‐rays. They exhibit ⊥ c cyanobridged layers of octahedra [M^III(CN)₆] and [M^IIN₄(OH₂)₂], which punctually are interconnected also || c to yield altogether a spaceous framework. The M^II atoms at the positions linking into the third dimension are only five‐coordinated and form square pyramids [M^IIN₅] with angles N–M^II–N near 104° and distances of Mn–N: 1 × 214, 4 × 219 pm; Cd–N: 1 × 220 resp. 222, 4 × 226 resp. 228 pm. Further details and structural relations within the family of Prussian Blue are reported and discussed.     

Cyanide‐Bridged Tetranuclear REIII2FeIII2 (RE = Y,Tb, Dy) Molecular Squares with 2, 2′:6′,2′′‐Terpyridine as a Capping Ligand

Self‐assembly reaction between hydrated rare‐earth (RE) nitrates RE(NO₃)₃ · 6H₂O with K₃Fe(CN)₆ in H₂O/DMF solution by employing the tridentate ligand 2, 2′:6′,2′′‐terpyridine (terpy) as a capping ligand has yielded three cyanide‐bridged compounds [RE(terpy)(DMF)(H₂O)₂][Fe(CN)₆] · 6H₂O [RE = Y ( 1 ), Tb ( 2 ), Dy ( 3 )]. FT‐IR spectra confirmed the presence of terpy ligands and cyanide groups in compounds 1 – 3 . Single‐crystal X‐ray structural analysis indicated that these compounds are isomorphous and adopt neutral [RE₂Fe₂] molecular squares, which are further linked through hydrogen bonding interactions to generate a three‐dimensional supramolecular network. Magnetic susceptibility measurements revealed that significant single ion magnetic anisotropy dominates the properties of these compounds.     

K⋅⋅⋅F/O Interactions Bridge Copper(I) Fluorinated Alkoxide Complexes and Facilitate Dioxygen Activation

Seven E[Cu(OR)₂] copper(I) complexes (E=K⁺, {K(18C6)}⁺ (18C6=[18]crown‐6), or Ph₄P⁺; R=C₄F₉, CPhMe^F₂, and CMeMe^F₂) have been prepared and their reactivity with O₂ studied. The K[Cu(OR)₂] species react with O₂ in a copper‐concentration‐dependent manner such that 2:1 and 3:1 Cu/O₂ adducts are observed manometrically at ?78 °C. Analogous reactivity with O₂ is not observed with the {K(18C6)}⁺ or Ph₄P⁺ derivatives. Solution conductivity data demonstrate that these K[Cu(OR)₂] complexes do not behave as 1:1 electrolytes in solution. The K⁺ ions induce aggregation of multiple [Cu(OR)₂]^? units through K???F/O interactions and thereby effect irreversible O₂ reduction by multiple Cu centers. Bond valence analyses for the potassium cations confirm the dominance of the fluorine interactions in the coordination spheres of K⁺ ions. Intramolecular hydroxylation of ligand aryl and alkyl C? H bonds is observed. Nucleophilic reactivity with CO₂ is observed for the oxygenated Cu complexes and a Cu^II carbonate has been isolated and characterized.     

Heterotrimetallic Coordination Polymers: {CuIILnIIIFeIII} Chains and {NiIILnIIIFeIII} Layers: Synthesis,Crystal Structures,and Magnetic Properties

The use of the [Fe^III(AA)(CN)₄]^? complex anion as metalloligand towards the preformed [Cu^II(valpn)Ln^III]³⁺ or [Ni^II(valpn)Ln^III]³⁺ heterometallic complex cations (AA=2,2′‐bipyridine (bipy) and 1,10‐phenathroline (phen); H₂valpn=1,3‐propanediyl‐bis(2‐iminomethylene‐6‐methoxyphenol)) allowed the preparation of two families of heterotrimetallic complexes: three isostructural 1D coordination polymers of general formula {[Cu^II(valpn)Ln^III(H₂O)₃(μ‐NC)₂Fe^III(phen)(CN)₂ {(μ‐NC)Fe^III(phen)(CN)₃}]NO₃ ? 7 H₂O}_n (Ln=Gd ( 1 ), Tb ( 2 ), and Dy ( 3 )) and the trinuclear complex [Cu^II(valpn)La^III(OH₂)₃(O₂NO)(μ‐NC)Fe^III(phen)(CN)₃] ? NO₃ ? H₂O ? CH₃CN ( 4 ) were obtained with the [Cu^II(valpn)Ln^III]³⁺ assembling unit, whereas three isostructural heterotrimetallic 2D networks, {[Ni^II(valpn)Ln^III(ONO₂)₂(H₂O)(μ‐NC)₃Fe^III(bipy)(CN)] ? 2 H₂O ? 2 CH₃CN}_n (Ln=Gd ( 5 ), Tb ( 6 ), and Dy ( 7 )) resulted with the related [Ni^II(valpn)Ln^III]³⁺ precursor. The crystal structure of compound 4 consists of discrete heterotrimetallic complex cations, [Cu^II(valpn)La^III(OH₂)₃(O₂NO)(μ‐NC)Fe^III(phen)(CN)₃]⁺, nitrate counterions, and non‐coordinate water and acetonitrile molecules. The heteroleptic {Fe^III(bipy)(CN)₄} moiety in 5 – 7 acts as a tris‐monodentate ligand towards three {Ni^II(valpn)Ln^III} binuclear nodes leading to heterotrimetallic 2D networks. The ferromagnetic interaction through the diphenoxo bridge in the Cu^II?Ln^III ( 1 – 3 ) and Ni^II?Ln^III ( 5 – 7 ) units, as well as through the single cyanide bridge between the Fe^III and either Ni^II ( 5 – 7 ) or Cu^II ( 4 ) account for the overall ferromagnetic behavior observed in 1 – 7 . DFT‐type calculations were performed to substantiate the magnetic interactions in 1 , 4 , and 5 . Interestingly, compound 6 exhibits slow relaxation of the magnetization with maxima of the out‐of‐phase ac signals below 4.0 K in the lack of a dc field, the values of the pre‐exponential factor (τ_o) and energy barrier (E_a) through the Arrhenius equation being 2.0×10^?12 s and 29.1 cm^?1, respectively. In the case of 7 , the ferromagnetic interactions through the double phenoxo (Ni^II–Dy^III) and single cyanide (Fe^III–Ni^II) pathways are masked by the depopulation of the Stark levels of the Dy^III ion, this feature most likely accounting for the continuous decrease of χ_M T upon cooling observed for this last compound.     

Solvent‐Dependent Dihydrogen/Dihydride Stability for [Mo(CO)(Cp*)H2(PMe3)2]+[BF4]− Determined by Multiple Solvent⋅⋅⋅Anion⋅⋅⋅Cation Non‐Covalent Interactions

Low‐temperature (200 K) protonation of [Mo(CO)(Cp*)H(PMe₃)₂] ( 1 ) by Et₂O ? HBF₄ gives a different result depending on a subtle solvent change: The dihydrogen complex [Mo(CO)(Cp*)(η²‐H₂)(PMe₃)₂]⁺ ( 2 ) is obtained in THF, whereas the tautomeric classical dihydride [Mo(CO)(Cp*)(H)₂(PMe₃)₂]⁺ ( 3 ) is the only observable product in dichloromethane. Both products were fully characterised (ν_CO IR; ¹H, ³¹P, ¹³C NMR spectroscopies) at low temperature; they lose H₂ upon warming to 230 K at approximately the same rate (ca. 10^?3 s^?1), with no detection of the non‐classical form in CD₂Cl₂, to generate [Mo(CO)(Cp*)(FBF₃)(PMe₃)₂] ( 4 ). The latter also slowly decomposes at ambient temperature. One of the decomposition products was crystallised and identified by X‐ray crystallography as [Mo(CO)(Cp*)(FH???FBF₃)(PMe₃)₂] ( 5 ), which features a neutral HF ligand coordinated to the transition metal through the F atom and to the BF₄^? anion through a hydrogen bond. The reason for the switch in relative stability between 2 and 3 was probed by DFT calculations based on the B3LYP and M05‐2X functionals, with inclusion of anion and solvent effects by the conductor‐like polarisable continuum model and by explicit consideration of the solvent molecules. Calculations at the MP4(SDQ) and CCSD(T) levels were also carried out for calibration. The calculations reveal the key role of non‐covalent anion–solvent interactions, which modulate the anion–cation interaction ultimately altering the energetic balance between the two isomeric forms.     

Di‐Benzo‐18‐Crown‐6 and its Derivatives as Ligands in the Search for Ion Channels

Based on the previously reported one‐dimensional channel system [(H₂O)?(DB18C6)(μ₂‐H₂O)_2/2][(H₃O)?(DB18C6)(μ₂‐H₂O)_2/2]I₃ ( 2 ), which is realized by stacking of crown ether molecules (DB18C6 = dibenzo‐18‐crown‐6), other synthetic approaches towards ionic channels and their results are presented in this paper. The “cutting out” approach using DB18C6 as scissor, applied on NaI, yields the compound [Na?(DB18C6)I(THF)][Na?(DB18C6)(H₂O)₂]I(THF)₂(CHI₃) ( 1 ), in high yield. It is based on a neutral and a cationic complex of sodium by DB18C6 linked via H‐bonding to give short chain fragments. The anion exchange approach, trying to replace I₃^? by Br₃^? leads to the intercalation of a cation into a DB18C6 chain in [(Me₃NPh)(DB18C6)]Br₃ ( 3 ). A similar reaction as for the synthesis of 2 , but replacing iodide with bromine, yields finally a brominated DB18C6 ligand. In the presence of iron, the compound [(H₅O₂)?(Br₄‐DB18C6)₂][FeBr₄], 4 , is observed, in which a H₅O₂⁺‐cation is encapsuled by two brominated crown ether molecules. The absence of Fe and an excess of Br₂ leads to the complexation of H₃O⁺, and co‐crystallisation of bromine in [(H₃O)?(Br₄‐DB18C6)]Br₃Br₂ ( 5 ).     

Post‐Synthetic Monovalent Central‐Metal Exchange,Specific I2 Sensing,and Polymerization of a Catalytic [3×3] Grid of [CuII5CuI4L6]⋅(I)2⋅13 H2O

From a predesigned grid, [Cu^II₅Cu^I₄L₆] ? (I)₂ ? 13 H₂O ( 1 ), in which LH₂ was a pyrazinyl‐triazolyl‐2,6‐substituted pyridine, we successfully synthesized an extended 3D complex, ¹_∞[{Cu^II₅Cu^I₈L₆}{μ‐[Cu^I₃(CN)₆]}₂ ? 2 CH₃‐ CN] ( 2 ), that displayed unprecedented coexistence of all the five known coordination geometries of copper. Grid 1 displayed monovalent central metal exchange (CME) of Cu^I for Ag^I for the first time, as well as the formation of tri‐iodide in the crystalline state. These systems were investigated for their magnetic properties. Remarkably, grid 1 showed much higher catalytic activity than the Ag‐exchanged product for synthesis of a substituted triazole, 1‐benzyl‐4‐phenyl‐1H‐1,2,3‐triazole.     

Syntheses,Structures and Electrochemistry Properties of Two Dicyanamide Manganese(III) Complexes [Mn(5‐Brsalen)(dca)]·CH3OH and [Mn(3‐Meosalphen)(dca)(H2O)]

Two manganese(III)‐dicyanamide compounds, [Mn(5‐Brsalen)(dca)] · CH₃OH ( 1 ) and [Mn(3‐Meosalphen)(dca)(H₂O)] ( 2 ) (dca = dicyanamide anion, [N(CN)₂]^–), were synthesized and characterized by elemental analysis, IR spectroscopy, single‐crystal X‐ray structure analysis, and cyclic voltammetry. The structure of complex 1 is an infinite zigzag chain of hexacoordinate Mn^III ions, in which the adjacent manganese atoms are connected by dca in μ_1,5‐bridging mode. The molecular structure of complex 2 consists of a hexacoordinate Mn^III atom, which generates a slightly distorted octahedral arrangement, and a dimer structure is formed by intermolecular hydrogen bonding interactions. The electrochemical properties of the two complexes were measured by cyclic voltammetry.